Palladium catalysed C–N bond formation in supercritical carbon dioxide has been accomplished. Carbamic acid formation is avoided in part through the use of an N-silylamine as the coupling partner. Employing a catalyst system of Pd₂dba₃ (1 mol%) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl (X-Phos) (2 mol%) enabled the catalytic amination of aryl bromides and chlorides with N-silylanilines to be realised in excellent yield. Extension of the methodology to the N-arylation of N-silyldiarylamines, N-silylazoles and N-silylsulfonamides is reported.